Process for producing electrolytic magnesium



July 11, 1939. s. L. MADORSKY PROCESS FOR PRODUCING ELECTROLYTIC IAGNESIUM Filed Jan. 25, 1938 Soil O A l?! C/ /0 part.

Patented Julyll, 1939 i l V I I i I um-mo sTATEs PATENT. oFFics 3 2,105,384 I I PROCESS FOR PRODUCING EIJC'I'BOLYTIC MAGNESIUM Samuel L. Madorsky, Washington, D. C. Application January 25, 1938, 8erlal' No. 186,89! io Claims. (on; topic) The present invention relates generally to the aflo'rdin'g aneasy and economical means of elimiextraction of metallic magnesium 'irom magnev nating injurious impurities. a slum bearing ores, such as dolomite, magneslte, A previous method of preparing anhydrous brucite, and containing magnesiumcarbonate or MgCla from magnesium ammonium chloride conmagnesium oxide or hydroxide or the like. More sists in preparing hydratedmagnesium amparticularly the present invention relates to such monium chl ride, M8C- 2-NH4 1 then heatprocesses in which the ore is treated' to" convert ing the MgCl2.NH4C1.6H2O to a temperature high the magnesium contents thereof into' hydrated enough to drive of! the water of hydration, but nesium ammonium chloride, this in turn bemateriallybelow the dissociation temperature, oi.

0 ing treated by a series of steps which converts M8Cl2.NH4C1, that isvto about 215-230" centi- 10 the same into anhydrous magnesium chloride, gr an then ociating the Mgcll-N the latter being then subjected to fused elecby introducing it in a bath of molten anhydrous trolysis to obtain metallic magnesium. MgClt' .I find, however, that on heating It is the main object of the presentinvention M8C12.NH4CL6H2'O, even to 175- centigrade, the to simplify the process above described'and to me] begins to v p ri before d the Water 15 reduce the cost of the same; of hydration is removed, thus exposingv the MgCl:

4 Another object of the present invention is to to the reaction with R to torm MgO and E01,, conduct the process above described in such a in accordance with the equation: I manner that the chlorine generated in the elec- 20 trolytic cell is;con'verted into'a hydrogen chloride (1) MgCh+H2o Mgo+2HQl 00111531111118 8 mixture which is employed d t- Besides, the method of vaporizing the NHlC'l from 1 1 t process 1 1;; gaseous 1 the MgChLNH4Cl by introducing the latter in a.

A further object or this invention is to utilize bath of molten s is difllwlt and uneconoml- I the chlorine, liberated in the electrolysis, in cal. In view of the fact that MEG]: has a melting nci nt d economical manner, point oi 708 centigrade and that the evapora- 25 Another object of this invention is to provide tion, me] d its dlmciatiqn into a highly efllcient' cyclic process for the prepara- N34 and H01 at 511011 a h p ature require tion of from magnesium ammonium eat deal h would have t chloride in which the metallic product oi elecmaintained at tempemtule above cellar 3o trolysis is recovered, and the gaseous. products grade" I are utilized to prepare the salt used in the elec- 4110151161 p e method o P l ,4

trolyti'c operation. v I hydrous MgClz from magnesium ammonium Still another object of invention is to pro- 011101-1118. mists 1n first firming the'dmlble vide a novel m t preparing gaseous MgChNILCLGEO, then heating this, double salt 35 tum-11mm! suitable for preparing my starting in a stream of air at a lower temperature until 35 material for electrolysis. v s fl z is o ai and fi y eat- A further object r this invention is to provide 8 the whm mmo at a hither temperaa novel-method oi decomposing m i. i ture, in a stream or. pure dry gaseous HCl, to tree 7 monium hl t 1 mg a anhydrous thg M8C1a from the NHlCl and the H20 simul-" 740 Mach. y taneously. o-

The ry m8nesiumb' dri such This application is a continuation in-p'art .ot dolomite. and brucite, cont i egg-1 my earlier application Serial No. 123,312, 'illed' v amountsoiealcium ig n a 1mm m January 30,1937, in which I have described a must he'separated from before the lat- 811111131 method of preparing metillll m lum I ter can be used for La irom'ordinary magnesium bearing ores. 45

. by dissolving the ore-jwlth hydrochloric acid and, The reason why pure dry gaseous H01 has-to adding tov the solution a sumcient-famount oi J e-used. 8 the mill and NHiCl to convert the 1180!: in the to tlmeously'lies in the tact thatthe'MgCl: and H20, .MgCltNmCl in solution. Is-ean Wang n. -in, the uacnumciamo are intimately asiron and aluminum as nomnnd anoint by W when h Ma -m heated 50 neutralizing the solution or m at a high temperature the men part reacts with Y monium hydroxide, and then mutate t the H20 part inthe same compound to form M80 cium as ($804 by adding to the. solution sul- I T 7 phuric acid or magnesium sulphate, withoutpre- (2) MgClzmCl2mO= 5s cipitating magnesium ammonium chloride, thus MgO-i-NBsCl-HHCH-EO By carrying out this heating step in a stream or Pure dry gaseous HCl this reaction is prevented from taking place.

The preparation of dry gaseous HCl, substantially free from other gases and water vapor, is an expensive and 'diflicult procedure. I flnd that ii I use substantially anhydrous MgClmNHcCl in the final step 'ofpreparing anhydrous MgCh, I can free the MgClaNH4C1 from NH4C1 by heating it in an atmosphere containing from about 2 to 20% by volume of gaseous HCl at temperatures between about 300-500 centigrade. The advantage of using an atmosphere having a low content of HCl lies in the following facts.

The easiest and cheapest way of converting the chlorine, resulting from the electrolysis of MgClz, into HCl, is to react this chlorine with steam and coke at an elevated temperature. The resulting as will contain carbon monomde and HCl in accordance with the equation:

(a) cn+mo+c=2nc1+co I I Since it is dimcult to feed into the converter the exact amount of steam required in the reaction with C12, the amount used should be in exess of the equivalent amount reacting with the Ch in order to insure complete conversion of the latterinto HCl. The excess H2O, not reacting with C12, will react .with the coke to give CO and H2, thus diluting the HCl in the gaseous mixture.

Aside from this, in the ordinary practice of electrolyzing fused MgCla, the chlorine coming oil at the anode is mixed with a large volume of air inorder to protect the apparatus, in which the hot chlorine is handled, from corrosion. This air admixed with the chlorine, on reacting with the coke in the gas producer, forms CO and CO2,

thus diluting the HCl containing gas still iurther with these gases and with nitrogen.

One of the objects of this invention is to provide an eilicient and economical method for producing the gaseous stream required in the step of removing 'NHiCl from anhydrous MgCLNHtCl. In previous attempts to convert the Cl: into H01 by reacting the C]: with steam and a solid carbonaceous fuel, the reaction was carried out under such conditions that the gaseous mixture contained, in addition to HCl, C0, C02 and N2. a substantial amount of water vapor. Moreover,

in the processes hitherto known, the gases generated by the gas producer were cooled and scrubbed for the absorption of the hydrogen chloride gas, and the hydrochloric acid thus obtained was subsequently treated in a series of steps so as to yield a stream ride gas.

In my process, a gas containing a small amount of gaseous HCl, say from 2 to 20%, but substantially free from H2O vapor, can be used in the step of preparing anhydrous MgCh from anhydrous MgClaN'H4Cl, the variation in the proportion of HCl in the gas depending upon temperature of operation of this step and degree of treedom of the gas from water vapor.

To obtain such a gaseous mixture, dry solid carbonaceous fuel, such as dry coke, is fed into a converter of the type used in making producer gas. A- mixture of C12, air and steam is passed thru the incandescent coke bed. The amount of steam used is in excess of the equivalent amount required to convert all of the C12 into HCl. The excess steam reacts with the coke to give 00 and H2, in accordance with the equation:

of pure dry hydrogen chlo- To insure complete, conversion of Cl: and H20 into HCl, CO and Hz, the fuel bed is kept hot and deep. The exact temperature and depth of the fuel bed will depend on the size of the converter and the amount of air and steam introduced with the chlorine. Under these conditions, the gas mixture will be free' from water first absorbing the HCl in water to separate it from the other gases, then removing it'from the water, drying and heating it to the proper temperature, are avoided.

Another object of this invention is to provide a novel and eflicient method of preparing an hydrous magnesium ammonium chlbride,

to be used in the final steps of preparing anhydrous MgClz. As was pointed out above, when MgCl:.NH4Cl.6H20 is heated the NH4C1 begins to vaporize before all of the water has vaporized, so that the MgClz is exposed and is free to react with the H20. v

To avoid. this difficulty, I use as the atmosphere for vaporizing and removing the HzOirom the MgClaNHsCLfiHaO, an atmosphere saturated with NH4C1 vapor, at a temperature of-about '160-220 centigrade. 1 Under .such conditions, where the atmosphere", is saturated with- NH4C1,

This dust is allowed to settle the NH4C1 in the magnesium ammonium chloride is prevented from vaporizing while the H20 is being vaporized, and the resulting product will be anhydrous MgChNI-LCI.

To obtain an atmosphere saturated with ammonium chloride vapor, the gaseous mixture, after it passes from the rotary kiln where the NH-iCl is vaporized from anhydrous MBCI2.NH4C1, at about 30045002 is cooled to about 220 centigrade to condense the bulk of the NHACI as a solid salt. The gas mixture, still containing gaseous M401, is then used as the M401 saturated atmosphere in the step of vaporizing 61-120 from MgClaNHrCLGHaO. to obtain anhydrous MEClaNHtCl and the ,HCl, prepared from the C12, in the preparation of new batches of magnesium ammonium chloride from an acid soluble basic magnesium compound, such as MgCOs, MgO, Mg(OH)2 and the like. 1

The gaseous mixture after passing thru the rotary kiln or similar container, where the 61120 i vaporized from the MgClr;NH4Cl.6l-Ir0, is washed or'scrubbed with water to remove from it NHiCl and HCl.

The HCl solution containing some NH4C1 is then reacted'with the acid soluble basic Mg compound to form M801: in solution. The condensed solid NH CI is then added to this solution to ram Mach-H3401 in solution. The magnesium ammonium chloride is then separated from the solution in the form of MgClaNHsOLBHaO by introducing. into the solution afurther amount v of concentratedhydrochloric acid and the ugchnmciemo is used in the preparation of anhydrous ucchmnci andthen anhydrous M8012. v

The following is a detailed description of my process. Anhydrous magnesium chloride is electrolyzed from. a fused bath in an electrolytic cell to obtain metallic Mg and C12. The hot Clz-is mixed, as it comesoif the anode, with air, and.

the mixture is passed together with steam thru an incandescent carbonaceous fuel bed in a gas? producer into which is fed dry coke. The re- 'sulting as mixture containing N2, 00,112.00: and HCl is then passed thru a dust settler or dust catcher and then, while still hot, at about soc-500 centigrade, thru a rotary kiln contain- The Nl-I Cl vaporizes and is carriedoif by the gaseous stream, and the anhydrous MgCh is transferred to the electrolytic cell.

The'gas mixture-containing the NHiCl vapor is cooled in a condenser .to about 220 centigrade to condense the M401 in the form of a solid salt. The gas mixture issuing from the condenser, while still saturated with NHiGl vapor at about 160-220 centigrade, ispassed thru a second rotary kiln containing MgClzNHrCLGHzO.

The 6H-.-O vaporizes as steam and the anhydrous MgCl2.NH4C1 is passed to the first rotary kiln to be heated; at the higher temperatureto obtain anhydrous MgClz.NH4Cl.

The gas mixture which in the meantime has cooled to about 160 centlgrade and still containing gaseous HCl and some unconde'nsed NHiCl, is washed or scrubbed with water to remove ,the HCl and nrnel in the form or an aqueous solution. The gas mixture, now free from NH4C1 and 'HCl, and containing N2, CO, H:-

[and CO2, is of the nature of producer gas and is used for various purposes, such as raisingsteam. to be used in the gas producer or to heat the electrolytic cell.

The HCl solution is transferred to the reaction l tank containing an acid soluble basic Mg compound, such as MgCOa, MgO, Mg(OH): and the like, where the reactions:

('0 M (on)=+'2nci=mch+2n=o preferably at 50-l00 centigrade, take place.

The condensed NH4C1 salt is then transferred to the reaction tank where it reacts with the MEC]: in solution to form MgClaNHeCl in solution. v Any silica present in the acid soluble mag nesium bearing material remains uhdissolved.

Any Fe, Al or similar metals present in the Mgbearing material as impurities, react with the Hill to form chlorides. These chlorides are precipitated as. hydroxides by neutralizing the solu- I tion in the reaction tankwith NH: or'NH40H.

Ca present in the Nlg bearing material as 'ir'iipurity is-precipitated in the same reaction tank as @1804, by means of m, or M8804 or (NHOSO. i J

wa I

The solution m the reaction tank is filtered;

. while still hot, from the precipitated impurities,

Fe(OH)=, A1(OH)3, CaSO4- and from the silica.

To the hot filtrate is then added some concentrated hydrochloric acid and the filtrate allowed .to cool. The crystals of MgChNH4GL6l-hOsettle liquor by decantatio'n. 'rhe' ngchnmclsmo crystalsare then treated toobtain' anhydro MgClaNHsCl, etc. as described above.

The mother liquor from the MgC1aNH4CL6H2O is really concentrated HCl acid and is used for salting out MgCl2NH4CL6H2O from the next batch of hydrochloric acid treated are, in the step where concentrated HCl acid is added to Fe(I-I)a, AliOI-Dz. and from the silica. 4

- to the bottom and are separated from the mother l5 the hot filtrate from the precipitated CaSO4,

Summarizing. now the various steps of the process and referring to the drawin anhydrous MgClz is electrolyzed from a fused bath in the cell A, them is tapp d in molten state at regular iritervalsjwhile the Cl: is mixed with air and the mixture passed together with steam into the gasproducer G, into which is also fed dry coke.

The gas mixture D is passed into the rotary kiln E where MgClmNI-LCI is decomposed into MgCh-and NH4C1. The MgClz B is passed into the'electrolytic cell A, while the gas mixture,

"containing the NH4C1in the form of a vapor,

is passedto a cooler H where Tt h bulk of the mixture J, saturated with NHiCl vapor, is-then passed into a" second rotary kiln G where MgClzNH4CL6HzO is dehydrated. The anhydiousYMgCl-rNHrCl is passed to the rotary kiln E,--while the gas mixture is passed to the scrubber I to remove from it HCl and NI-lrCl. The producer gas, freed from HCl and NH4C1, is then removed to a gas holder, while the aqueous solution of HCl-and NH4C1 is transferred to F v where with MgCla in solution to form MgCl2.NH4Cl in solution. Concentrated HCl acid is then introduced into F to salt out MgClmNH4CL6H2O. The mother liquor is decanted and the Mgchmncwmo I tion to utilize any single step by itself or to combine any orall of these operations in any desired sequence.

"I claim: v V 4 1. The process of preparing metallic magne sium from substantially anhydrous magnesium ammonium chloride which comprises decomposing said magnesium ammonium chloride by contacting it at elevated temperatures with a gaseous mixture produced by passing electrolytic chlorine incandescent carbonaceous {material to produce a mixture containing hydrogen chloride and gaseous products of combustion and reaction substantially free from water vapor, forming substantially: anhydrous magnesium chloride and ammonium chloride vapor thereby, and electrolyzing the substantially anhydrous magnesium chloride in a fused bath to produce metallic-magnesium and chlorine. I

NH4C1 condenses as a drysolid salt;- The gas 40 'it reacts with a Mg bear ng ore. The solid NH4C1 is then transferred from.H to F, where it reacts togetheiawith' steam and air through a bed of 2. The process of claim 1 in which the ammonium chloride vapor, together with the hydrogen chloride from the step of decomposing magnesium ammonium chloride is contacted in aqueous solution with acid' soluble magnesium,

bearing ore to form magnesium ammonium chloride.

3. The method of extracting magnesium .from magnesium bearing ores comprising the steps of contacting said ores with hydrochloric acid and ammonium chloride to form magnesium ammo-- the magnesium chloride in a fused bath to produce metallic magnesium and chlorine.

4. The method according to claim 3, in which the hydrated magnesium ammonium chloride is dehydrated by heating in an atmosphere saturated with ammonium chloride obtained during the decomposition of magnesium ammonium chloride.

5. The method according to claim 3 in which the gaseous mixture containing ammonium chloride and hydrogenchloride from the step of decomposing magnesium ammonium chloride is contacted in aqueous solution with'magnesium bearing ore to form magnesium ammonium chloride.

6. The cyclic process for the production of I magnesium which comprises subjecting substantially anhydrous magnesium chloride to electrolysis in a molten bath to produce metallic magnesium and chlorine, passing the chlorine together with steam and air through a bed of incandescent carbonaceous material to form a mixture of gaseous hydrogen chloride and other gaseous products of combustion and reaction, but substantially free from water vapor, contacting the gaseous mixture with anhydrous magnesium ammonium chloride at elevated temperatures to convert the latter into substantially anhydrous magnesium chloride by removing the ammonium chloride in the form of a vapor, and electrolyzing the substantially anhydrous magnesium chloride in a molten bath to produce metallic magnesium and a further supply of chlorine.

7. The cyclic process for the production of magnesium which comprises subjecting substantially anhydrous magnesium chloride to electrolysis in a molten bath -passing the chlorine liberated in the electrolysis together with air and steam, through a bed of incandescent carbonaceous material to obtain a mixture of gaseous hydrogen chloride and other gaseous products of combustion' and reaction, controlling the depth of the fuel bed and the proportions of chlorine, air and steam, and the amount of moisture in the fuel, to insuresubstantially complete interaction of chlorine, steam, air and carbon to form a gaseous mixture comprising hydrogen chloride, hydrogen, carbon monoxide, nitrogen and somecarbon dioxide, contacting the gaseous mixture with substantially anhydrous magnesium ammonium chloride at elevated temperatures to convert the latter into substantially anhydrous magnesium chloride by removing the ammonium chloride in the form of a vapor, and electrolyzing the substantially anhydrous magnesium chloride in a molten bath to produce metallic magnesium and chloride.

8. The cyclic process for the production of magnesium which comprises subjecting substantially anhydrous magnesium chloride to electrolysis in a molten bath, passing the chlorine liberated in the electrolysis together with steam and air, through a bed of incandescent carbonaceous material to form a mixture of hydrogen chloride and other gaseous products of combustion and reaction, but substantially free from water vapor, bringing the gaseous mixture into contact with substantially anhydrous magnesium ammonium chloride at elevated temperatures to convert the latter into substantially anhydrous magnesium chloride while removing the ammonium chloride in the form of a vapor, cooling the gaseous mixture to a temperature sufllcient to condense a major portion of the ammonium chloride in the form of a solid salt, bringing the aseous mixture, while still hot and saturated with ammonium chloride vapors at the lower temperature into contact with hydrated magnesium ammonium chloride to convert the latter into substantially anhydrous magnesium ammonium chloride by removing the water associated with it in the form of water vapor, contacting an aqueous solution of the hydrogen chloride and ammonium chloride in the gaseous mixture remaining from the dehydration step with an acid soluble oxygen containing compound of magnesium together with the ammonium chloride condensed after the decomposition of the magnesium ammonium chloride to form hydrated magnesium ammonium chloride, dehydrating the hydrated salt to obtain substantially anhydrous magnesium ammonium chloride for the conversion to substantially anhydrous magnesium chloride for the electrolytic step.

9. The cyclic process for the production of magnesium which comprises subjecting substantially anhydrous magnesium chloride to electrol-,

ysis in a molten bath, feeding the chlorine pro-' duced thereby together with steam and air into a suitable gas producer operated on solid car-- bonaceous fuel to obtain a mixture of products of combustion and reaction and gaseous hydrogen chloride, butYsubstantially free from water vapor, contacting the gaseous mixture, while it is still hot, with substantially anhydrous magnesium ammonium chloride at a temperature of about 300-500 centigrade to vaporize and carry off ammonium chloride, separating the major part of the ammonium chloride from the gaseous mixture through condensation by cooling to about -2 20 centigrade, contacting the gaseous mixture saturated with ammonium chloride vapor at this temperature with hydrated magnesium ammonium chloride to remove the water of hydration separating the ammonium chloride and hydrogen. chloride from'the gaseous mixture in' the form of an aqueous solution, reacting the solution and the condensed ammonium chloride with an acid soluble magnesium bearing ore tov obtain hydrated magnesium ammonium chloride, dehydrating said hydrated compound to form substantially anhydrous magnesium ammonium chloride, and decomposing said anhydrous comnound to form ammonium chloride and anhydrous magnesium chloride.

10. The process nesium from magnesium bearing ores which comprises contacting said ores with hydrochloric acid so1ution, adding ammonium chloride to the resulting ore solution to form mag esium ammonium chloride, separating said -magnesium ammonium chloride in the form of its hydrated compound, dehydrating said hydrated compound to form substantially anhydrous magnesium am'-',

monium chloride, contacting said magnesium for extracting metallic magammonium chloride in sclid state at elevated temperatures with a substantially moisture-free gaseous atmosphere containing hydrogen chloride to decompose it into substantially anhydrous magnesium chloride and ammonium chloride vapor, contacting said ammonium chloride with the magnesium bearing ore in hydrochloric acid solution to form afurther supply of magnesium ammonium chloride, and electrolyzing the magnesium chloride in a fused bath to form metallic o magnesium.

- SAMUEL L. HADORSKY. 

